Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PRODUCTION OF ALUMINUM FOIL CAPACITOR ELECTRODES
This invention relates to production of aluminum
foil capacitor electrodes, and more particularly to a pro-
cess ~herein etched and cleaned foil is thermally treated
at about 595 to 650C and then anodized in an adipate
electrolyte which may also contain a phosphate. The pro-
cess is particularly useful in making low-voltage foil,
i.e. foil for use at less than 100V, and specifically 0-60V
foil.
It has been known in the prior art to thermally
treat aluminum electrolytic capacitor foil. Cold rolled
(hard) foil is thermally treated (anneal~ed) to reduce its
brittleness. Aluminum foil has also been heat treated in
the prior art to produce a more crystalline oxide, and it
has also been heat treated during anodization to stabilize
it.
Most of these prior art processes are conducted
well below the melting point of aluminum, except for the
anneal~ing process during which there is crystal reorgani-
zation and growth.
Anodization of aluminum capacitor foil in both
phosphate and dicarboxylic salt electrolytes is well-known
also. To produce the barrier layer type anodic oxide,
salts of the C4 - C10 dicarboxylic acids are generally
preferred, with the lower acids, and specifically adipates,
finding more favor because they are more soluble and have
good anodization efficiency.
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Various electrolyte systems and various heat
treatment schemes ha~e been tried in efforts to improve
capacitance. In some combinations, it was found that
heat treatment reduced capacitance of low-voltage foils,
even though it improved capacitance for intermediate and
high-voltage foils.
Randall, ~guyen and Hutchins describe in
US 4,470,885 issued September 11, 1984 the treatment of
etched foil with a phosphate solution followed by heat
treatment at 590 to 630C to form a thermal oxide layer
which modifies the subsequently formed barrier oxide layer.
This process described by Randall et al is directed to
foils formed at intermediate to high voltages, e.g. lOOV
and above.
A feature of the present invention is a process
directed to improving capacitance at low anodization
voltages, e.g. at less than lOOV and specifically 0-60V.
In general, the process of this invention features
the heat-treatment of etched, clean aluminum capacitor foil
at about 595 to 650C and then anodization of the foil in
an adipate electrolyte to improve low-voltage capacitance,
e.g., less than lOOV and specifically 0-60V. The anodiza-
tion electrolyte may contain a phosphate or the final
anodization step may be carried out in a phosphate anodi-
zation electrolyte.
Aluminum foil melts at about 675C; therefore,
the heat treatment of this invention is carried out for
up to at most 90 sec. near 595C, and for at most 30 sec.
at 650C. This process of heat treatment combined wi-~h
anodization in an adipate electrolyte improves low-voltage
capacitance by 30 to 60%, with the greatest improvement
being at lower voltages, e.g., 30V, compared to foil which
had not been heat-treated.
The foil must be clean for the obvious reason
that any residue will be baked onto the surface and into
the etch structure of the foil. The cleaning material
must remove or displace residual chloride ions from the
etching process, and in turn either be completely
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volatilized or form a residue which is innocuous as far as
electrolytic capacitors are concerned. Organic reagents
which will selectively displace chloride ions, e.g., citric
acid or citrates, or inorganic acids such as nitric or
phosphoric acid, have been used as cleaning agents.
A small amount of phosphate is incorporated into
the anodization electrolyte of the final anodization
(reanodization) stage is carried out in a phosphate elec-
trolyte to impart hydration resistance to the foil. As
is well-known, aluminum foil bearing a barrier layer anodic
oxide is very sensitive to moisture and will react with it,
even from the ambient atmosphere, forming a hydrated oxide
which will reduce the capacitance of the foil. It has
become common to anodize aluminum capacitor foil to the
desired voltage, stabilize the foil, and then reanodize
to the desired voltage (to heal any defects) in an elec-
trolyte which will impart hydration resistance. The foil
can then be stored without capacitance change before being
made into capacitors.
Low-voltage capacitance, specifically that in
the 0-60V range, is increased by the process of this inven-
tion wherein etched and cleaned aluminum electrolytic capa-
citor foil is heat treated at about 595 to 650C and then
anodized in an adipate electrolyte which may contain a
phosphate.
The adipate may be an alkali metal or ammonium
salt, such as sodium or ammonium adipate. Other dicar-
bo~ylic acid salts known to be useful as anodizing elec-
trolytes were tried but gave an unstable anodized foil
when subjected to the heat treatment followed by anodi-
zation, for example, azelaic, glutaric and succinic acid
salts. Ammonium dihydrogen phosphate was also evaluated,
but did not give the capacitance increase obtained with
the adipate electrolyte.
With heat-treatment temperatures up to about
595C, foi.l anodized in a phosphate electrolyte or an
adipate electrolyte displayed about the same capacitance
at 10V and 30V formations. Above 595C, anodization in
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the adipate electrolyte gave a 30 to 60% capacitance
increase in the 0-60V formation range, with the largest
increase for 30V formation. Thus, the process of this
invention is useful for increasing capacitance of foil
intended for low-voltage capacitors.
Since other known dicarboxylic acid anodizing
electrolytes produce either unstable foil or foil with
lower capacitance when used following a heat treatment
at 595 to 650C, it would appear that there is a syner-
gistic effect in the combination of the heat treatmentand formation in an aqueous adipate electrolyte. This
apparent synergism is reinforced by the difference in
results obtained with adipate vs. phosphate formation.
The capacitances parallel each other at heat treatment
temperatures up to about 540C when they begin to di-
verge. At about 595C, the capacitance subsequently
obtained with an aqueous adipate formation is signifi-
cantly higher than with a phosphate formation.
Example 1
This example shows the difference in adipate
versus a standard phosphate formation following heat
treatment at 538C and above. At the lower end of the
range, heat-treatments were carried out for 45 to
135 sec., but only up to 40 sec. at the highest tempera-
ture used. The phosphate electrolyte was 0.1% ammonium
dihydrogen phosphate (ADP) and the adipate was 5% di-
ammoni~lm adipate (DAA). The foil was 2.6 mil thick
aluminum foil which had been etched and cleaned and ano-
dized to 10, 30, 60 and lOOV.
The capacitance at each voltage is given in
~F/in2 of foil area, temperature is in C, and time is
in seconds. The anodization was carried out at each vol-
tage level at 88C and 360 mA/in2 (projected area)
current density.
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Comparative data are ~iven below for 45 sec.
at the lower heat-treatment temperature and 30 sec. at
the upper end of the range.
Table 1
Heat Treatment Capacitance
Electrolyte Temp. Time lOV 30V 60V lOOV
ADP 538 45 336 117 51 25
593 45 334 125 57 28
649 30 319 149 66 29
DAA 538 45 372 129 65 33
593 45 367 138 70 33
649 30 400 167 72 31
- There is little difference in lOOV capacitance at any
heat treatment level, but a large difference at lower
voltages both with respect to heat treatment level and
formation electrolyte. At about 595C, a treatment time
of up to 90 sec. is preferred; while at about 650C, the
time should be no more than 40 sec. and, preferably, is
30 sec. so that foil will not start to soften and melt.
Example 2
This example shows the difference for three
different etched aluminum foils which have been anodized
as above in the adipate electrolyte with or without heat-
treatment. The first two foils are commercial DC etched
foils, and the third is an AC etched foil. Heat-treatment
was carried out at 649C for 30 sec.
Table 2
Capacitance
FoilHeat-treatment lOV 30V 60VlOOV
1 No 489 148 73 40
Yes 479 195 87 39
% increase -2 32 19 -2.5
2 No 410 140 77 40
Yes 430 190 85 38
% increase 5 36 10 -5%
3 No 395 110 58 30
Yes 400 167 72 31
% increase 1 52 24 3
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There was little change in lOV or lOOV capacitance, but
a large changè~above lOV t ~ 60V. Although this pro-
cess is most suitable for.~ 10 to 60V range, production
lines are generally set up in lOOV or multiples of lOOV
ranges. Therefore, this process will most likely be used
for 0 to lOOV foil.
Capacitor foil which has been anodized in an
adipate or other dicarboxylate electrolyte will pick up
moisture and hydrate upon standing or storage. To pre-
vent this, a small amount of phosphate is added to theanodization electrolyte. Alternatively, the final
reanodization, after stabilizing or depolarizing the
foil, is carried out in a phosphate electrolyte to heat
the film and impart hydration resistance.
When the phosphate is incorporated into the
main anodization electrolyte, 0.002 to 0.09% of phosphate
is used. When the phosphate is used as the final elec-
trolyte, an aqueous 0.05 to 0.5% solution is used. While
any soluble phosphate may be used, monosodium or mono-
ammonium phosphate is preferred.
Generally, an aqueous solution containing 5%
adipate as formation electrolyte is preferred, but
0.5 to 12% may be used.
